Recently, Cd-free wide-gap CuInS2-based 'CIS' thin film solar cells with a [Zn(S,O)/ZnS] bi-layer instead of a CdS buffer were developed, which (after post-annealing) showed comparable power conversion efficiencies as CdS-buffered references. To elucidate whether the heat treatment changes the electronic structure of the [Zn(S,O)/ZnSYCIS heterointerface, which could explain the performance improvement, we have investigated corresponding structures by X-ray and UV photoelectron as well as optical spectroscopy before and after post-annealing. A heat-treatment-induced increase of the band bending in the CIS absorber could be identified, which correlates with an improved open circuit voltage of respective solar cells after post-annealing. (c) 2006 Elsevier B.V. All rights reserved.